Low-temperature hydrogen production from oxygenated hydrocarbons

Abstract

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.

1. A method of producing hydrogen comprising:
 reacting water and a water-soluble oxygenated hydrocarbon selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, alditols, and mixtures thereof, at a pressure of from about 0.1 atm to about 53.29 atm; 
 in the presence of a catalyst comprising an alloy, mixture, or combination of at least one Group VIII transition metal and a metal selected from the group consisting of silver, gold, Group IIB metals, Group VIIB metals, Group IVA metals, and Group VA metals; and 
 wherein the catalyst is adhered to a support. 
 
     
     
       2. The method of  claim 1 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, boron nitride, and mixtures thereof. 
     
     
       3. The method of  claim 1 , wherein the support is a zeolite. 
     
     
       4. The method of  claim 1 , wherein the support is a carbon nanotube or a fullerene. 
     
     
       5. The method of  claim 1 , further comprising reacting the water and the water-soluble oxygenated hydrocarbon in the presence of a water-soluble salt of an alkali or alkaline earth metal. 
     
     
       6. The method of  claim 5 , wherein the water-soluble salt is an alkali or an alkaline earth metal hydroxide, carbonate, nitrate, or chloride salt. 
     
     
       7. The method of  claim 1 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols. 
     
     
       8. The method of  claim 1 , wherein the catalyst comprises a metal selected from the group consisting of nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, and mixtures thereof. 
     
     
       9. The method of  claim 1 , wherein the catalyst comprises ruthenium, palladium, or platinum. 
     
     
       10. The method of  claim 1 , wherein the catalyst comprises a metal selected from the group consisting of Group IIB metals, and Group VIIB metals. 
     
     
       11. The method of  claim 1 , wherein the catalyst comprises a metal selected from the group consisting of zinc, germanium, tin, and bismuth. 
     
     
       12. The method of  claim 11 , wherein the catalyst comprises rhenium. 
     
     
       13. The method of  claim 1 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol and glycerol, and the at least one Group VIII transition metal(s) is selected from the group consisting of palladium and platinum. 
     
     
       14. The method of  claim 1 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of sucrose, glucose, mannitol, and sorbitol. 
     
     
       15. The method of  claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the condensed liquid phase. 
     
     
       16. The method of  claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the vapor phase. 
     
     
       17. The method of  claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 450° C. 
     
     
       18. The method of  claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 275° C. 
     
     
       19. The method of  claim 1 , wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali metal compounds, and alkaline earth compounds. 
     
     
       20. A method of producing hydrogen comprising:
 reacting water and a water-soluble oxygenated hydrocarbon selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, alditols, and mixtures thereof, at a pressure of from about 0.1 atm to about 53.29 atm; 
 in the presence of a catalyst comprising at least one metal selected from the group consisting of palladium, platinum, mixtures thereof, combinations thereof, and alloys thereof, and in the presence of a water-soluble salt of an alkali or alkaline earth metal; 
 wherein the catalyst is adhered to a support. 
 
     
     
       21. The method of  claim 20 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, boron nitride, and mixtures thereof. 
     
     
       22. The method of  claim 20 , wherein the support is a zeolite. 
     
     
       23. The method of  claim 20 , wherein the support is a carbon nanotube or a fullerene. 
     
     
       24. The method of  claim 20 , wherein the water-soluble salt is an alkali or an alkaline earth metal hydroxide, carbonate, nitrate, or chloride salt. 
     
     
       25. The method of  claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols. 
     
     
       26. The method of  claim 20 , wherein the catalyst comprises platinum. 
     
     
       27. The method of  claim 20 , wherein the catalyst further comprises a metal selected from the group consisting of silver, gold, Group IIB metals, and Group VIIb metals. 
     
     
       28. The method of  claim 20 , wherein the catalyst further comprises a metal selected from the group consisting of zinc, germanium, tin, and bismuth. 
     
     
       29. The method of  claim 20 , wherein the catalyst comprises rhenium. 
     
     
       30. The method of  claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol and glycerol. 
     
     
       31. The method of  claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of sucrose, glucose, mannitol, and sorbitol. 
     
     
       32. The method of  claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the condensed liquid phase. 
     
     
       33. The method of  claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the vapor phase. 
     
     
       34. The method of  claim 20 , wherein the catalyst further comprises nickel or ruthenium. 
     
     
       35. The method of  claim 20 , wherein the catalyst comprises more than one Group VIII transition metal. 
     
     
       36. The method of  claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 450° C. 
     
     
       37. The method of  claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 275° C. 
     
     
       38. The method of  claim 20 , wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali metal compounds, and alkaline earth compounds.